Thermal stability and decomposition mechanism analysis of 1, 1’-Azobis(cyclohexanecarbonitrile) by STA, DSC, ARC and TG-FTIR

Abstract

1, 1′-Azobis(cyclohexanecarbonitrile) (ABCN) is a kind of azo compound, which is widely used as an initiator in the polymer industry. Plenty of heat will be released during the thermal decomposition, and fire or explosive accidents could happen when the cooling system of the polymerization reactor fails. In this manuscript, the thermal decomposition behavior of ABCN under a dynamic temperature environment was investigated by simultaneous thermogravimetric analyzer (STA). Differential scanning calorimeter (DSC) was used to detect the thermal effects of different stages of mass loss. The apparent activation energy was calculated by Kissinger-Akahira-Sunose methods (K-A-S methods). The thermal runaway behavior was investigated by accelerating rate calorimeter (ARC), which was used to predict time to maximum rate under adiabatic condition (TMRad). The results show that the temperatures at TMRad = 8 h and 24 h are 93.0 °C and 89.7 °C, respectively. The self-accelerating decomposition temperature (SADT) is 86.6 °C, which is calculated based on the thermal theory of Semenov. Since ABCN is used at 60–90 °C, a major accident could happen when the heat accumulated in the reactor is not removed timely. The risk of thermal runaway reactions for ABCN was defined against the risk matrix as level Ⅲ, which is an unacceptable risk. The carbon radicals and nitrogen were released during the decomposition of ABCN based on the experiment result of thermal gravimetric analyzer-Fourier transform infrared spectrometer (TG-FTIR) system. Several safety assessment parameters could supply references for the industry to alleviate thermal hazards and prevent critical incidents.